Gold decorated NaYF<Subscript>4</Subscript>:Yb,Er/NaYF<Subscript>4</Subscript>/silica (core/shell/shell) upconversion nanoparticles for photothermal destruction of BE(2)-C neuroblastoma cells

Gold decorated NaYF₄:Yb,Er/NaYF₄/silica (core/shell/shell) upconversion (UC) nanoparticles (~70–80 nm) were synthesized using tetraethyl orthosilicate and chloroauric acid in a one-step reverse microemulsion method. Gold nanoparticles (~6 nm) were deposited on the surface of silica shell of these core/shell/shell nanoparticles. The total upconversion emission intensity (green, red, and blue) of the core/shell/shell nanoparticles decreased by ~31% after Au was deposited on the surface of silica shell. The upconverted green light was coupled with the surface plasmon of Au leading to rapid heat conversion. These UC/silica/Au nanoparticles were very efficient to destroy BE(2)-C cancer cells and showed strong potential in photothermal therapy.     

Emergent Upconversion Sustainable Micro‐Optical Trapping Device

Ultrathin‐thickness single‐junction Si‐based solar cells can be developed to enhance photoelectric conversion efficiency (PECE) approaching to Shockley–Queisser limit. However, loss of short circuit current is a crucial factor that dramatically affects PECE improvement. Even though many studies have focused on rare reflector architecture for facilitating near‐infrared radiation absorption, PECE is still constraint due to its fabrication cost. Herein, an upconversion sustainable micro‐optical trapping device is reported. Using a systematic procedure, a high upconversion performance core–shell‐nanoparticles (CSNPs) structure is synthesized. Accordingly, silica diatom microporous frustule is a good electromagnetic field localization chamber, upon which CSNPs are embedded through a microassemble synthesis. This emerging device can be support on ultrathin‐thickness single‐junction Si‐based solar cells as a rare absorber with its low preparation cost. In the experiment, CSNPs upconversion optical density by surface plasmon resonance of Au nanoparticle's enhancement can be increased five‐time greater than NaYF₄ without SiO₂ coating. A finite difference time domain simulation and real color luminescence images in this study are also demonstrated.     

Construction of a Dual Drug Carrier on the Basis of Hollow Structured Upconversion Nanoparticles for pH‐Responsive Drug Delivery and UCL/MRI Dual Mode Imaging

A series of Gd³⁺ doping hollow upconversion nanoparticles NaYF₄:Yb,Gd,Tm (h‐UNCP) are prepared successfully. The hollow NaYF₄:Yb,Gd,Tm possess excellent upconversion luminescence (UCL) and large longitudinal relativity (r₁ = 128.3 mm ^?1 s^?1), which can be potentially used for UCL/magnetic resonance imaging (MRI) dual mode imaging. On the basis of the optimal h‐UCNP, doxorubicin hydrochloride (DOX) and methotrexate (MTX) are used as drug models to prepare a dual drug carrier. After the encapsulation of DOX on the h‐UCNP, chitosan (CS) is further wrapped and then used to load MTX to obtain a dual drug carrier h‐UCNPs/DOX/CS/MTX. The pH responsive release of DOX and MTX is discussed. The MTX release climbs from 33% to 100% by regulating the pH from 5.8 to 7.4. The DOX release is different at different pH conditions. The synergistic effect of DOX and MTX on the cancer cells is confirmed by cell viability. The h‐UCNPs/DOX/CS/MTX are tracked by cells UCL imaging and vivo MRI imaging. The excellent performance of UCL imaging and positive MRI images demonstrates that h‐UCNPs/DOX/CS/MTX can be used for UCL/MRI dual mode imaging. All the results show the potential application of h‐UCNPs/DOX/CS/MTX in pH responsive release and UCL/MRI dual imaging.     

共沉淀法制备NaYF4 : Tm3+,Yb3+的上转换发光

通过共沉淀法制备Tm³⁺和Yb³⁺掺杂的NaYF₄上转换发光材料。其中Tm³⁺和Yb³⁺的摩尔分数分别为0.01%,0.1%。在室温下测试了NaYF₄ : Tm³⁺,Yb³⁺材料在300~1 100 nm的吸收光谱。利用X射线衍射(XRD),扫描电镜(SEM)测试了合成材料的物相结构和微观形貌。结果表明:NaYF₄ : Tm³⁺,Yb³⁺材料为六方相晶体,其颗粒大小约为50~60 nm,产物结晶良好,含有少量杂相。在798 nm近红外光激发下,测试了样品的上转换发光光谱。观察到了蓝、绿色上转换发光。讨论了上转换发光的可能机理,蓝光主要来源于Tm³⁺的激发态¹G₄到基态³H₆的跃迁,绿光来源于Tm³⁺的¹D₂→³H₅跃迁。     

NIR‐Triggered Release of Nitric Oxide with Upconversion Nanoparticles Inhibits Platelet Aggregation in Blood Samples

There is a great challenge to overcome the limitation of tissue penetration depth, while maximizing the benefit of light‐triggered biochemical cascades in a well‐defined mode simultaneously. Here, a new method of near‐infrared (NIR) light‐triggered release of nitric oxide (NO) by developing upconversion nanoparticles (UCNPs)‐based conjugate chemistry is reported. As the key nanotransducer in the design, core–shell‐structured UCNPs are encapsulated with a layer of SiO₂ and then covalently linked with a potent NO‐releasing donor (S‐nitroso‐N‐acetyl‐dl ‐penicillamine, SNAP). It is featured with highly localized breakage of chemical bonds of SNAP molecules by NIR–UV upconversion, enabling simultaneous NO release in a light dosage‐dependent manner. The biological effects of NO releasing are demonstrated by cellular imaging and inhibition of platelet aggregation from blood samples. This work provides a flexible and robust platform to generate cell‐signaling gas molecules trigged by NIR laser with deep tissue penetration.     

Avidin conjugation to up-conversion phosphor NaYF4:Yb3+, Er3+ by the oxidation of the oligosaccharide chains

NaYF₄:Yb³⁺, Er³⁺ nanoparticles were successfully prepared by a polyol process using diethyleneglycol (DEG) as solvent. After being functionalized with SiO₂–NH₂ layer, these NaYF₄:Yb³⁺, Er³⁺ nanoparticles can conjugate with activated avidin molecules (activated by the oxidation of the oligosaccharide chain). The as-formed NaYF₄:Yb³⁺, Er³⁺ nanoparticles, NaYF₄:Yb³⁺, Er³⁺ nanoparticles functionalized with amino groups, avidin conjugated amino-functionalized NaYF₄:Yb³⁺, Er³⁺ nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM), Fourier transform infrared (FT-IR), UV/Vis absorption spectra, and up-conversion luminescence spectra, respectively. The biofunctionalization of the NaYF₄:Yb³⁺, Er³⁺ nanoparticles has less effect on their luminescence properties, i.e., they still show the up-conversion emission (from Er³⁺, with ⁴S_3/2 → ⁴I_15/2 at ~540 nm and ⁴F_9/2 → ⁴I_15/2 at ~653 nm), indicative of the great potential for these NaYF₄:Yb³⁺, Er³⁺ nanoparticles to be used as fluorescence probes for biological system.     

High Quantum Yield Single‐Band Green Upconversion in La2O3:Yb3+, Ho3+ Microcrystals for Anticounterfeiting and Plastic Recycling

Single‐band green upconversion (UC) with high green purity and color stability is urgently required for plastic recycling and anticounterfeiting. However, it is very difficult to obtain single‐band green emission for benchmark Yb³⁺/Er³⁺ activated UC materials (such as NaYF₄:Yb³⁺,Er³⁺) due to the strong accompanying red UC. Herein, highly efficient and stable single‐band green UC is reported in La₂O₃:Yb³⁺/Ho³⁺ (LYH) microcrystals with record high absolute UC quantum yield (UCQY) of 2.6% for single‐band green UC. LYH yields pure green UC with large and stable intensity ratio, I_Green/I_Red ≈ 18. LYH presents not only higher UCQY for a single‐band green UC but also much more pure and stable green UC than the benchmark UC materials such as NaYF₄:Yb³⁺,Er³⁺ and Gd₂O₂S:Yb³⁺,Er³⁺. These results suggest that the newly developed LYH can, in principle, be promising for anticounterfeiting and plastic recycling. Its proof‐of‐concept is demonstrated as a security label based on a transparent institute logo.     

Dextran‐Coated Antiferromagnetic MnO Nanoparticles for a T1‐MRI Contrast Agent with High Colloidal Stability

A simple approach to synthesize carboxymethyl dextran‐coated MnO nanoparticles (CMDex‐MnONPs) with high colloidal stability in physiological saline solutions is described here for potential applications as a magnetic resonance imaging (MRI) T₁ contrast agent. The thermal decomposition methodology is used to produce uniform MnONPs with an average size of around 20 nm, and its hydrophobic surface is modified with CMDex molecules, conferring hydrophilic properties. After CMDex coating, the nanoparticle presents high colloidal stability in concentrations ranging from 10 to 50 μg mL^?1, average hydrodynamic size (Z‐average) of 130 nm, polydispersity degree of ≈12%, and negative surface charge in both simulated body fluid solutions and pure water with zeta‐potential of –20 and –40 mV, respectively. The CMDex‐MnONPs with 20 nm show antiferromagnetic behavior at room temperature, and the magnetic properties are found to be strongly dependent of the nanoparticle size, increasing the contribution of the ferromagnetic Mn₃O₄ phase with decreasing size for nanoparticles about 3 nm. Cytotoxicity evaluation in cancerous and noncancerous cells in the range of 5.0–50.0 μg mL^?1 shows low toxicity for cancerous cells and lack of the same for healthy cells lines. Related to the magnetic properties, CMDex‐MnONP presents significant r₁ relaxivity and low r₂/r₁ relaxivity ratio. The results suggest that these nanoparticles display characteristics for potential applications as an MRI T₁ contrast agent.     

Colloidal Crystals of NaYF4 Upconversion Nanocrystals Studied by Small‐Angle X‐Ray Scattering (SAXS)

Spherical NaYF₄ upconversion nanocrystals with mean radii of about 5 and 11 nm are observed to form colloidal crystals, i.e., 3D assemblies of the particles with long‐range order. The colloidal crystals of the larger particles form directly in solution when dispersions of the particles in toluene are stored at room temperature for several weeks. Crystallization of the smaller particles takes place when their dispersions in hexane are slowly dried at elevated temperatures. The formation and the structure of the colloidal crystals are studied by small‐angle X‐ray scattering (SAXS). SAXS measurements show that the smaller as well as the larger particles assemble into a face‐centered cubic lattice with unit cell dimensions of a = 18.7 nm and a = 35.5 nm, respectively. The SAXS data also show that the particles in the colloidal crystals still bear a layer of oleic acid on their surfaces. The thickness of this layer is 1.5–1.8 nm, as determined by comparing the unit cell dimensions of the colloidal crystals with the mean particle sizes. The latter could be very precisely determined from the distinct oscillations observed in the SAXS data of dilute colloidal dispersions of the nanocrystals.     

Core–shell nanophosphor with enhanced NIR–visible upconversion as spectrum modifier for enhancement of solar cell efficiency

A distinct enhancement of upconversion luminescence from core to core/shell (C/S) structure under low flux near infrared (NIR) excitation at 976 nm has been achieved in lanthanide (Er³⁺, Yb³⁺)-doped NaYF₄ core with undoped NaYF₄ shell nanoparticles (NP). A green chemistry approach has been taken to synthesize monodisperse monophasic C/S NP with the core (~20 nm) and shell (~5 nm) crystallizing into cubic phase. Hydrophobic C/S NP have been further made hydrophilic by coating a transparent SHMP layer without affecting luminescence. C/S (NaYF₄: Er, Yb/NaYF₄) NP integrated dye-sensitized solar cell indicated 11.9% enhancement in overall conversion efficiency under AM 1.5 conditions, due to NIR–visible spectrum modification by fluorescent NPs. The results indicate great potential of such upconverting C/S nanophosphor in solar cell applications.     

Effects of surface functionalization of hydrophilic NaYF<Subscript>4</Subscript> nanocrystals doped with Eu<Superscript>3+</Superscript> on glutamate and GABA transport in brain synaptosomes

Specific rare earth doped nanocrystals (NCs), a recent class of nanoparticles with fluorescent features, have great bioanalytical potential. Neuroactive properties of NaYF₄ nanocrystals doped with Eu³⁺ were assessed based on the analysis of their effects on glutamate- and γ-aminobutyric acid (GABA) transport process in nerve terminals isolated from rat brain (synaptosomes). Two types of hydrophilic NCs were examined in this work: (i) coated by polyethylene glycol (PEG) and (ii) with OH groups at the surface. It was found that NaYF₄:Eu³⁺-PEG and NaYF₄:Eu³⁺-OH within the concentration range of 0.5–3.5 and 0.5–1.5 mg/ml, respectively, did not influence Na⁺-dependent transporter-dependent l-[¹⁴C]glutamate and [³H]GABA uptake and the ambient level of the neurotransmitters in the synaptosomes. An increase in NaYF₄:Eu³⁺-PEG and NaYF₄:Eu³⁺-OH concentrations up to 7.5 and 3.5 mg/ml, respectively, led to the (1) attenuation of the initial velocity of uptake of l-[¹⁴C]glutamate and [³H]GABA and (2) elevation of ambient neurotransmitters in the suspension of nerve terminals. In the mentioned concentrations, nanocrystals did not influence acidification of synaptic vesicles that was shown with pH-sensitive fluorescent dye acridine orange, however, decreased the potential of the plasma membrane of synaptosomes. In comparison with other nanoparticles studied with similar methodological approach, NCs start to exhibit their effects on neurotransmitter transport at concentrations several times higher than those shown for carbon dots, detonation nanodiamonds and an iron storage protein ferritin, whose activity can be registered at 0.08, 0.5 and 0.08 mg/ml, respectively. Therefore, NCs can be considered lesser neurotoxic as compared to above nanoparticles.     

Influence of Shell Formation on Morphological Structure,Optical and Emission Intensity on Aqueous Dispersible NaYF4:Ce/Tb Nanoparticles

A highly water-dispersible NaYF₄:Ce/Tb (core), NaYF₄:Ce/Tb@NaYF₄(core/shell) and NaYF₄:Ce/Tb@NaYF₄@SiO₂ (core/shell/SiO₂) nanoparticles (NPs) were synthesized via a general synthesis approach. The growth of an inert NaYF₄ and silica shell (~14 nm) around the core-NPs resulted in an increase of the average size of the nanopaticles as well as broadening of their size distribution. The optical band-gap energy slightly decreases after shell formation due to the increase the crystalline size. To optimize the influence of shell formation a comparative analysis of photoluminescence properties (excitation, emission, and luminescence decay time) of the core, core/shell, and core/shell/SiO₂ NPs were measured. The emission intensity was significantly enhanced after inert shell formation around the surface of the core NPs. The Commission International de l’Eclairage chromaticity coordinates of the emission spectrum of core, core/shell, core/shell/SiO₂ NPs lie closest to the standard green color emission at 545 nm. By quantitative spectroscopic measurements of surface-modified core-NPs, it was suggested that encapsulation with inert and silica layers was found to be effective in retaining both luminescence intensity and dispersibility in aqueous environment. Considering the high aqueous dispersion and enhanced luminescence efficiency of the core-NPs make them an ideal luminescent material for luminescence bioimaging and optical biosensors.     

Biocompatible Lipid‐Coated Persistent Luminescent Nanoparticles for In Vivo Imaging of Dendritic Cell Migration

Dendritic cell (DC)‐based vaccines for immunotherapy have already achieved promising results in the last decade. To further improve current treatment protocols and enhance the therapeutic outcome, noninvasive in vivo tracking of DCs remains of crucial importance. Persistent luminescent nanoparticles (PLNPs) are inorganic materials which show an afterglow for hours after the optical excitation has ceased. If the afterglow is in the near‐infrared, the emission of injected particles can be tracked in vivo. However, stability and toxicity issues limit the use of bare PLNPs for biological applications. Therefore, appropriate surface functionalization is needed to improve their biocompatibility. In this study, it is demonstrated that near‐infrared light emitting LiGa₅O₈:Cr³⁺ nanoparticles can be functionalized with a biocompatible lipid coating which provides them with outstanding stability in biological media. In vitro experiments show efficient uptake, absence of cytotoxicity even at very high particle concentrations, and no adverse effects on the maturation potential of DCs. DCs labeled with lipid‐coated LiGa₅O₈:Cr³⁺ nanoparticles injected in mice can be imaged over days, confirming efficient in vivo migration to the popliteal lymph node. Together the results show that lipid coated LiGa₅O₈:Cr³⁺ nanoparticles possess excellent possibilities for further use in research and development of DC based vaccines.     

Enhancing up conversion luminescence effect of β-NaYF<Subscript>4</Subscript>: Yb<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> by Li<Superscript>+</Superscript> ion doped approach

Up-conversion (UC) is a photoluminescence process which converts few low energy photons to a higher energy photon. This process has more potential usages in many different fields like bioimaging, solar spectrum tuning, and security encoding. Nowadays, researches about UC mostly focusing on biomedical signory and synthesis of nanoparticles. The synthesis of NaYF₄ nanoparticles executed under series of pH value condition results in different morphology and photoluminescence effect. Samples in low pH value created better consequent and quality than the specimen which had higher pH value. In addition, we observed NaYF₄ samples of doping Li⁺, realizing that the action of distorting in the local symmetry around rare-earth ions is caused by Li⁺ doping. The NaYF₄ microparticles which doped higher concentration of Li⁺ has strong fluorescence properties and intensities compared with their corresponding group of Li⁺-free, the blue emission 479 nm luminescence intensities and 454 nm luminescence intensities in NaYF₄:Yb³⁺, Tm³⁺ microparticles doped 20 mol% Li⁺ are enhanced 3 and 8 times, separately. And violet emission luminescence intensities around 345 and 360 nm are about 10 and 7 times, respectively. The result indicated that the improved UC luminescence of NaYF₄:Yb³⁺. Tm³⁺ microparticles with Li⁺ doping have potentially applications.     

Analysis of Upconversion Fluorescence Dynamics in NaYF4 Codoped with Er3+ and Yb3+

The efficiency of upconversion fluorescence for Er³⁺ and Yb³⁺ codoped into NaYF₄ powder crystals is investigated. The dependence of Er³⁺ green (540 nm) and red (660 nm) upconversion fluorescence intensities on laser excitation intensity and the ratio of the green and red fluorescence intensities respectively under 355‐nm and 936‐nm excitations have been measured and analyzed in terms of radiative and nonradiative relaxation mechanisms. It is shown that the intensity of both the green and red upconversion fluorescence bands is affected at high pumping intensities by a low‐lying state acting as a bottleneck, with the red fluorescence less affected than the green. In addition to two‐photon, two‐step excitation and energy transfer processes, nonlinear optical coupling mechanisms of avalanche processes appear responsible for reducing the bottleneck saturation of the red upconversion fluorescence.     

The water‐promoted Diels–Alder reaction in quaternary ammonium salts

Prevailing classification of salts based on their effect in solubility and stability of proteins in aqueous solution predicts that tetraalkylammonium salts, guanidinium chloride (GnCl), LiClO₄ act as salting‐in (S/I) and LiCl, NaCl act as salting‐out (S/O) in aqueous conditions. In the same context the behaviour of GnCl, LiClO₄ and LiCl are contradictory in polar solvents like ethylene glycol and formamide. In these solvents, expected salt effect shows just opposite nature from their usual expectation. However, in the aqueous solution salts like tetraalkylammonium halide (R₄NX, R = alkyl group, X = Br group) behave like salting‐in salts. The physicochemical origin of the salting in effect of R₄NX type of salts has been discussed elaborately in the present work. The role of cations in terms of substitution of various alkyl groups on R₄NX has been systematically presented here on the basis of experimental kinetic and thermodynamic studies. The abnormal behaviour of R₄NX salts in aqueous solution has also been explained by the Setschenov equation (k_s) and Δμ_solvation values, which highlights their individual nature out of common properties of R₄NX. Copyright © 2015 John Wiley & Sons, Ltd.     

Water‐Soluble Monolayer Molybdenum Disulfide Quantum Dots with Upconversion Fluorescence

Uniform water‐soluble monolayer MoS₂ quantum dots (MQDs) with lateral sizes of ≈2.1 nm, a clearly zigzag‐terminated edge, and a hexagonal lattice structure are achieved using ammonium molybdate, thiourea, and N‐acetyl‐l ‐cysteine (NAC) as precursors and the capping reagent in a facile one‐pot hydrothermal approach. MQDs have good dispersity and high stability in aqueous suspension and exhibit a significantly larger direct bandgap (3.96 eV) compared to monolayer MoS₂ nanosheets (1.89 eV). Pronounced blue‐shifts in the wavelengths of both the excitonic absorption and intrinsic state emission with activated strong luminescence at room temperature beyond monolayer MoS₂ nanosheets is demonstrated. Unusual upconversion photoluminescence is also observed and is caused by two successive transfers of energy from the near‐infrared (NIR) absorption generated by the NAC capping reagent to the hexagonal structure of MQDs. Additional optical properties of MQDs may provide numerous exciting technological applications. Here, MQDs are demonstrated as a highly selective fluorescent reagent for detecting tetracycline hydrochloride under UV and NIR irradiation.     

Synergistic upconversion effect in NaYF4:Yb,Tm nanorods under dual excitation of 980 nm and 808 nm

NaYF₄:Yb³⁺,Tm³⁺ nanorods are prepared with hydrothermal method. The upconversion luminescent properties are investigated under dual excitation of 980 nm and 808 nm. The blue emission is observed at about 475 nm under dual excitation. The intensity is 2.6 times higher than the total intensity of the two corresponding single wavelength excitations, showing a synergistic upconversion effect occurring there. The dual wavelength excitation not only effectively decreases non-radiative relaxation pumped by 980 nm but also reduces the rate of the back energy transfer from Tm³⁺ to Yb³⁺ pumped by 808 nm. The result provides a possible new way to further improve the upconversion efficiency of rare earth doped phosphor.     

A Nano‐Micro Hybrid Structure Composed of Fe7S8 Nanoparticles Embedded in Nitrogen‐Doped Porous Carbon Framework for High‐Performance Lithium/Sodium‐Ion Batteries

Iron sulfides are attractive anode materials for lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs) due to their high theoretical capacities, low cost, and eco‐friendliness. However, their real application is greatly hindered by the rapid capacity fading caused by the large volume changes and sluggish kinetics of iron sulfides during the charge and discharge processes. Combining with carbonaceous materials and tuning the structure at nanoscale are essential to address this issue. Here, a facile hydrothermal method coupled with a carbonization process is developed to synthesize a nano‐micro hybrid porous structure, which is composed of Fe₇S₈ nanoparticles embedded in nitrogen‐doped carbon framework (Fe₇S₈@NC‐PS). This hierarchical sphere is constructed by interconnected 2D nanowalls. The as‐prepared Fe₇S₈@NC‐PS electrodes reveal excellent rate capability and cycling stability in LIBs and SIBs. The remarkable electrochemical properties are attributed to the porous nano‐micro hybrid architecture and the high conductivity and structural stability of the nitrogen‐doped carbon framework.     

Dye‐Sensitized Core/Shell Upconversion Nanoparticles for Detecting Nitrites in Plant Cells

A fluorescent nanoprobe is reported for rapid detection of nitrites (NO₂^?) in plant cells. The probe is fabricated by linking neutral reds (NR) to the surface of upconversion fluorescent core/shell nanocrystalline with the bridging of polyethylene glycol (PEG) molecules. The fluorescence of upconversion nanoparticles (UCNPs) is stored by NR through fluorescence resonance energy transfer (FRET) under 980 nm excitation that can be released by further linking to NO₂^?. It is observed that the intensity rate of green to red emission of NR‐modified UCNPs changes linearly with increasing the amount of NO₂^?. So that concentration of NO₂^? can be accordingly addressed. Worth mentioning is that, comparing with bare core upconversion nanoparticles (NPs), core/shell UCNPs can greatly reduce the surface quenching of the fluorescence induced by solvents instead of NR and thus leading to the enhancement of signal‐to‐noise ratios. Moreover, excitation of core/shell UCNPs requires only a much lower power (0.06 W cm^?2) than bare cores which is beneficial to reducing the decomposition of NR to stabilize the FRET processes. Under the optimum conditions, the detection limit of nitrite in plant cells was 0.1 µg mL^?1.